Compositions and methods for controlling insects which damage rice and other crops

ABSTRACT

Compositions and methods for controlling insect populations, in particular, insects which attack rice crops, are disclosed. The compositions include one or more compounds from the Formula 1A and one or more compounds from the formulas 1B-G described in the specification, and optionally but preferably include a suitable carrier.

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application is a division of copending application Ser. No.09/660,777, filed Sep. 13, 2000, now allowed, which claims the benefitof provisional Application No. 60/153,837, filed Sep. 14, 1999,incorporated by reference herein in their entireties and relied upon.

FIELD OF THE INVENTION

[0002] This invention is generally in the area of compositions andmethods for controlling insects which damage rice and other crops. Moreparticularly, this invention relates to pesticidal compositionscomprising ethiprole and indoxacarb or structurally related compounds,and methods for using the compositions to treat rice crops for pestssuch as Nilaparvata lugens (brown planthoppers), Cnaphalocrocismedinalis (rice leaf rollers), and Nephotettix spp. (rice leaf hoppers),for example, Nephotettix cincticeps (green leaf hopper), the most commoninsects which attack rice crops.

BACKGROUND OF THE INVENTION

[0003] Rice crops are often attacked by pests such as Nephotettix spp.(rice leaf hoppers), such as Nephotettix cincticeps (green leaf hopper),Nilaparvata lugens (brown planthoppers) and Cnaphalocrocis medinalis(rice leaf rollers). Significant research efforts have been carried outto develop insecticidal compositions useful for controlling these pests.

[0004] It is very difficult to control insect pests which belong toHomoptera such as planthoppers, leafhoppers, aphids and whitefliesbecause of their specific ecological and physiological character traitsand also due to the rapid development of drug-resistant insects. Thereare currently few methods to effectively control such insect pests.

[0005] U.S. Pat. No. 5,082,860 to Karrer, et al. discloses using ethyl2-[4-(3,5-difluorophenoxy)phenoxy]ethylcarbamate to control cicadaswhich damage rice crops. However, it is unclear whether the carbamate isuseful in treating green leaf hoppers, brown planthoppers and rice leafrollers.

[0006] Frequently, several insecticides are effective against one ormore of the above insects, but not all of them. Accordingly, the use ofa single insecticide is often insufficient to protect crops of usefulplants adequately against pests. For example, indoxacarb is notparticularly effective against brown planthoppers, but is active againstgreen leaf hoppers and rice leaf rollers.

[0007] It would be advantageous to provide new compositions and methodsfor controlling cicadas and other insects which damage rice and othercrops. The present invention provides such compositions and methods.

SUMMARY OF THE INVENTION

[0008] Compositions and methods for controlling insect populations, inparticular, insects which attack rice crops, are disclosed. Thecompositions include one or more compounds from the Formula 1A and oneor more compounds from the formulas 1B-G, and optionally but preferablyinclude a suitable carrier.

[0009] The compounds of Formula IA-G are intended to include allgeometric and stereoisomers, agriculturally suitable salts thereof,agricultural compositions containing them and their use for the controlof insects in both agronomic and non-agronomic uses. The term“compounds” will be understood to include all such isomers and saltsthereof.

[0010] E is selected from the group H and C₁-C₃ alkyl; or

[0011] Y is selected from the group H; C₁-C₆ alkyl, benzyl; C₂-C₆alkoxyalkyl; C₂-C₆ alkenyl; C₂-C₆ alkynyl; C₁-C₆ alkyl optionallysubstituted by halogen, C₁-C₃ alkoxy, C₁-C₃ haloalkoxy, —CN, —NO₂,S(O)_(r)R³², COR³², CO₂R³², phenyl optionally substituted by halogen,—CN, C₁-C₂ haloalkyl and C₁-C₂ haloalkoxy; C₃-C₆ cycloalkyl; C₃-C₆cyclohaloalkyl; C₃-C₆ cycloalkylalkyl; —CHO; C₂-C₆ alkylcarbonyl; C₂-C₆alkoxycarbonyl; C₂-C₆ haloalkylcarbonyl; COR³⁶; CO₂R³⁶; C₁-C₆ alkylthio;C₁-C₆ haloalkylthio; phenylthio; R¹²OC(O)N(R¹³)S— and R¹⁴(R¹⁵)NS—;

[0012] R¹ and R² are independently selected from the group H, C₁-C₆alkyl, C₁-C₆ haloalkyl, C₂-C₆ alkenyl, C₂-C₆ haloalkenyl, C₂-C₆ alkynyl,C₃-C₆ haloalkynyl, C₂-C₆ alkoxyalkyl, C₂-C₆ alkylthioalkyl, C₁-C₆nitroalkyl, C₂-C₆ cyanoalkyl, C₃-C₈ alkoxycarbonylalkyl, C₃-C₆cycloalkyl, C₃-C₆ halocycloalkyl, halogen, —CN, —N₃, —SCN, —NO₂, —OR¹⁷,—SR¹⁷, —S(O)R¹⁷, —S(O)₂R¹⁷, —OC(O)R¹⁷, —OS(O)₂R¹⁷, —CO₂R¹⁷, —C(O)R¹⁷,—C(O)NR¹⁷R¹⁸, —SO₂NR¹⁷R¹⁸, —NR¹⁷R¹⁸, —NR¹⁸C(O)R¹⁷, —OC(O)NHR¹⁷,—NR¹⁸C(O)NHR¹⁷, —NR¹⁸SO₂R¹⁷, phenyl optionally substituted with 1 to 3substituents independently selected from W, and benzyl optionallysubstituted with 1 to 3 substituents independently selected from W; orwhen m or n is 2, (R¹)₂ can be taken together, or (R²)₂ can be takentogether as —OCH₂ O—, —OCF₂O—, —OCH₂CH₂O—, —CH₂C(CH₃)₂O—, —CF₂CF₂O or—OCF₂CF₂O— to form a cyclic bridge; provided that when R¹ or R² isS(O)R¹⁷, S(O)₂R¹⁷, OC(O)R¹⁷ or OS(O)₂R¹⁷ then R¹⁷ is other than H;

[0013] R³ is selected from the group H, J, —N₃, —NO₂, halogen,—N(R²²)R²³, C(R³⁴)═N—O—R³⁵, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₂-C₆ alkenyl,C₂-C₆ haloalkenyl, C₂-C₆ alkynyl, C₂-C₆ alkoxylalkyl, C₃-C₈alkoxycarbonylalkyl, —CO₂R¹⁷, —OR¹⁹, —C(O)R¹⁷, —C(O)NR¹⁷R¹⁸,—C(S)NR¹⁷R¹⁸, —C(S)R¹⁷, —C(S)SR¹⁷, —CN, Si(R²¹)(R²⁹)R²⁷, —SR²⁷,—S(O)R²⁷, —SO₂R²⁷, —P(O)(OR²⁷)₂, phenyl, phenyl substituted with(R¹⁶)_(p), benzyl and benzyl substituted with 1 to 3 substituentsindependently selected from W; or R³ is C₂-C₆ epoxyalkyl optionallysubstituted with a group selected from C₁-C₃ alkyl, —CN, —C(O)R²⁴,—CO₂R²⁴ and phenyl optionally substituted with W; or R³ is C₁-C₆ alkylsubstituted with a group selected from —C(O)N(R²⁵)R²⁶, —C(O)R²⁵, —SR²⁷,—S(O)R²⁷, —SO₂R²⁷, —SCN, —CN, C₁-C₂ haloalkoxy, —Si(R²⁸)(R²⁹)R³⁰,N(R²²)R²³, ONO₂, —OC(O)R²⁵, —P(O)(OR²⁷)₂ and J;

[0014] J is selected from the group saturated, partially unsaturated oraromatic 5- or 6-membered heterocyclic ring, bonded through carbon ornitrogen, containing 1-4 heteroatoms independently selected from thegroup consisting of 0-2 oxygen, 0-2 sulfur and 0-4 nitrogen, thissubstituent optionally containing one carbonyl and optionallysubstituted with one or more members selected from W;

[0015] R⁴ is selected from the group H, C₁-C₄ alkyl, COR²⁰ and C₂-C₄alkoxycarbonyl; or

[0016] R¹² is C₁-C₆ alkyl;

[0017] R¹³ is C₁-C₄ alkyl;

[0018] R¹⁴ and R¹⁵ are independently C₁-C₄ alkyl; or

[0019] R¹⁴ and R¹⁵ can be taken together as —CH₂CH₂CH₂CH₂CH₂— or—CH₂CH₂OCH₂CH₂—;

[0020] R¹⁶ is selected from the group C₁-C₆ alkyl, C₁-C₆ haloalkyl,C₂-C₆ alkenyl, C₂-C₆ haloalkenyl, C₂-C₆ alkynyl, C₃-C₆ haloalkynyl,C₂-C₆ alkoxyalkyl, C₂-C₆ alkylthioalkyl, C₁-C₆ nitroalkyl, C₂-C₆cyanoalkyl, C₃-C₈ alkoxycarbonylalkyl, C₃-C₆ cycloalkyl, C₃-C₆halocycloalkyl, halogen, CN, N₃, SCNNO₂, OR¹⁷, SR¹⁷, S(O)R¹⁷, S(O)₂R¹⁷,OC(O)R¹⁷, OS(O)₂R¹⁷, CO₂R¹⁷, C(O)R¹⁷, C(O)N R¹⁷R¹⁸, SO₂NR¹⁷R¹⁸, NR¹⁷R¹⁸,NR¹⁸C(O)R¹⁷, OC(O)NHR¹⁷, NR¹⁸C(O)NHR¹⁷, NR¹⁸SO₂R¹⁷, phenyl optionallysubstituted with 1 to 3 substituents independently selected from W, andbenzyl optionally substituted with 1 to 3 substituents independentlyselected from W; or when p is 2, (R¹⁶)₂ can be taken together as—OCH₂O—, —OCF₂O—, —OCH₂CH₂O—, —CH₂C(CH₃)₂O—, —CF₂CF₂O or —OCF₂CF₂O— toform a cyclic bridge; provided that when R¹⁶ is S(O)R¹⁷, S(O)₂R¹⁷,OC(O)R¹⁷ or OS(O)₂R¹⁷ then R¹⁷ is other than H;

[0021] R¹⁷ is selected from the group H, C₁-C₆ alkyl, C₁-C₆ haloalkyl,C₂-C₆ alkenyl, C₂-C₆ haloalkenyl, C₂-C₆ alkynyl, C₃-C₆ haloalkynyl,C₂-C₆ alkoxyalkyl, C₂-C₆ alkylthioalkyl, C₁-C₆ nitroalkyl, C₂-C₆cyanoalkyl, C₃-C₈ alkoxycarbonylalkyl, C₃-C₆ cycloalkyl, C₃-C₆halocycloalkyl, and optionally substituted phenyl and benzyl wherein thesubstituents are 1 to 3 substituents independently selected from W;

[0022] R¹⁸ is selected from the group H and C₁-C₄ alkyl; or

[0023] R¹⁷ and R¹⁸, when attached to the same atom, can be takentogether as —(CH₂)₄—, —(CH₂)₅—, or —CH₂CH₂OCH₂CH₂—;

[0024] R¹⁹ is selected from the group H, C₁-C₄ alkyl, C₂-C₄ alkenyl,C₂-C₄ alkynyl, C₂-C₄ alkylcarbonyl, C₂-C₄ alkoxycarbonyl and C₁-C₄alkylsulfonyl;

[0025] R²⁰ is C₁-C₃ alkyl;

[0026] R²¹ is selected from the group H, C₁-C₄ alkyl, C₂-C₄ alkenyl andC₂-C₄ alkynyl;

[0027] R²² is selected from the group H, C₂-C₇ alkylcarbonyl, C₂-C₇alkoxycarbonyl, optionally substituted C₁-C₄ alkyl, optionallysubstituted C₂-C₄ alkenyl, and optionally substituted C₂-C₄ alkynyl, thesubstituents selected from C₁-C₂ alkoxy, CN, C(O)R³⁰ and C(O)₂R²⁷;

[0028] R²³ is selected from the group H, C₁-C₃ alkyl, phenyl, phenylsubstituted with W, benzyl and benzyl substituted with W;

[0029] R²⁴ is selected from the group H, C₁-C₄ alkyl, C₂-C₄ alkenyl andC₂-C₄ alkynyl;

[0030] R²⁵ and R²⁶ are independently selected from the group H and C₁-C₂alkyl;

[0031] R²⁷ is selected from the group C₁-C₃ alkyl, phenyl and phenylsubstituted with W;

[0032] R²⁸ is C₁-C₃ alkyl;

[0033] R²⁹ is C₁-C₃ alkyl;

[0034] R³⁰ is selected from the group H, C₁-C₃ alkyl, phenyl and phenylsubstituted by W;

[0035] R³² is selected from the group C₁-C₃ alkyl;

[0036] R³⁴ is selected from the group H, Cl, C₁-C₄ alkyl, C₁-C₄ alkoxy,C₁-C₂ thioalkyl and CN;

[0037] R³⁵ is selected from the group H, C₁-C₄ alkyl, C₂-C₃alkylcarbonyl and C₂-C₃ alkoxycarbonyl;

[0038] R³⁶ is selected from the group phenyl and phenyl substituted withW;

[0039] W is selected from the group halogen, CN, NO₂, C₁-C₂ alkyl, C₁-C₂haloalkyl, C₁-C₂ alkoxy, C₁-C₂ haloalkoxy, C₁-C₂ alkylthio, C₁-C₂haloalkylthio, C₁-C₂ alkylsulfonyl and C₁-C₂ haloalkylsulfonyl;

[0040] m is 1 to 3;

[0041] n is 1 to 3;

[0042] p is 1 to 3;

[0043] r is 0, 1 or 2;

[0044] t is 2 or 3; and

[0045] u is 1 or 2.

[0046] Exemplary values of J include:

[0047] R^(1′) is S(O)_(m′)R^(5′);

[0048] R² is selected from a hydrogen atom, a halogen atom,—NR^(6′)R^(7′), —S(O)_(n′)R^(8′), C(O)R^(8′), C(O)OR^(9′), alkyl,haloalkyl, —OR^(9′), or —N═C(R^(10′))(R^(11′));

[0049] R^(3′) is selected from a halogen atom or the hydrogen atom;

[0050] R^(4′) is selected from a halogen atom, haloalkyl, haloalkoxy,—S(O)_(p′)CF₃, or —SF₅;

[0051] R^(5′) is alkyl or haloalkyl;

[0052] R^(6′) and R^(7′) are independently selected from a hydrogenatom, alkyl, haloalkyl, —C(O) R^(8′), C(O)OR^(8′), —S(O)_(q′)CF₃; thealkyl portions of which are optionally substituted by one or moreR^(12′); or R^(6′) and R^(7′) are joined so as together form a divalentradical having 4 to 6 atoms in the chain, this divalent radical beingalkylene, alkyleneoxyalkylene or alkyleneaminoalkylene, preferably toform a morpholine, pyrrolidine, piperidine or piperazine ring;

[0053] R^(8′) is alkyl or haloalkyl;

[0054] R^(9′) is selected from alkyl, haloalkyl or the hydrogen atom;

[0055] R^(10′) is selected from R^(9′) or alkoxy;

[0056] R^(11′) is alkyl or haloalkyl; or is selected from phenyl orheteroaryl that is optionally substituted by one or more groups selectedfrom hydroxy, halogen, alkoxy, —S(O)_(r′)R^(8′), cyano, R^(8′) orcombinations thereof;

[0057] R^(12′) is selected from cyano, nitro, alkoxy, haloalkoxy,—S(O)_(s)-alkyl, —S(O)_(s′)-haloalkyl, —C(O)-alkyl, —C(O)-haloalkyl,—C(O)O-alkyl, —C(O)O-haloalkyl, aminocarbonyl, alkylaminocarbonyl,dialkylaminocarbonyl, hydroxy, aminosulfonyl, alkylaminosulfonyl ordialkylaminosulfonyl;

[0058] X′ is selected from the nitrogen atom, or the radical C—R^(13′);

[0059] R^(13′) is a halogen atom;

[0060] R^(14′) is —C(O)CH₃ or —CN; and

[0061] m′, n′, p′, q′, r′ and s′ represent, independently of oneanother, the values zero, one or two;

[0062] Unless otherwise specified alkyl and alkoxy groups have from oneto eight, preferably one to four carbon atoms. The haloalkyl andhaloalkoxy groups likewise preferably have one to four carbon atoms. Thevarious individual aliphatic hydrocarbon moieties, that is, radicals andportions thereof (for example the alkyl moiety of alkylaminocarbonyl andalkylaminosulfonyl) have up to four carbon atoms in the chain.

[0063] The haloalkyl and haloalkoxy groups can bear one or more halogenatoms.

[0064] The term heteroaryl refers to a five to seven memberedheterocyclic ring containing from one to four heteroatoms selected fromnitrogen, oxygen and sulfur.

[0065] The term halogen means F, Cl, Br or I. The term “halo” before thename of a radical means that this radical is partially or completelyhalogenated, that is to say, substituted by F, Cl, Br or I, in anycombination, preferably by F or Cl.

[0066] R^(2′) is preferably an amino group, which is unsubstituted orwhich bears one or two substituents selected from the group consistingof alkyl, —C(O)R^(8′) and —C(O)OR^(8′); the alkyl portions of which areoptionally substituted by one or more R^(12′).

[0067] R^(3′) is preferably a halogen atom; especially preferred is achlorine atom;

[0068] R^(4′) is preferably selected from a halogen atom, haloalkyl,haloalkoxy, or —SF₅; especially preferred are CF₃—, CF₃O— and —SF₅.

[0069] R^(5′) is preferably methyl, ethyl or propyl.

[0070] A particularly preferred group of compounds of general formula(I) because of their systemic aphicidal properties are those wherein:

[0071] R^(2′) is NR^(6′)R^(7′);

[0072] R^(3′) is halogen;

[0073] R^(4′) is CF₃—, CF₃O— or —SF₅;

[0074] R^(5′) is alkyl;

[0075] X is CR^(13′);

[0076] R^(13′) is halogen; and

[0077] m′ is 0 or 1.

[0078] Preferred compounds are those wherein:

[0079] R¹ is selected from the group H, C₁-C₆ alkyl, C₁-C₆ haloalkyl,C₂-C₆ alkenyl, C₂-C₆ haloalkenyl, C₂-C₆ alkynyl, C₃-C₆ haloalkynyl,C₂-C₆ alkoxyalkyl, C₂-C₆ alkylthioalkyl, C₁-C₆ nitroalkyl, C₂-C₆cyanoalkyl, C₃-C₈ alkoxycarbonylalkyl, C₃-C₆ cycloalkyl, C₃-C₆halocycloalkyl, halogen, CN, SCN, NO₂, OR¹⁷, SR¹⁷, SO₂R¹⁷, CO₂R¹⁷,C(O)R¹⁷, phenyl optionally substituted with 1 to 3 substituentsindependently selected from W, and benzyl optionally substituted with 1to 3 substituents independently selected from W; with one R¹ substituentin the 4-position, or when m is 2 then (R¹)2 can be taken together as—CH₂C(CH₃)₂O—, —OCH₂CH₂O—, —OCF₂CF₂O—, or —CF₂CF₂O— to form a 5- or6-membered fused ring;

[0080] R² is selected from the group H, C₁-C₆ alkyl, C₁-C₆ haloalkyl,C₂-C₆ alkenyl, C₂-C₆ haloalkenyl, C₂-C₆ alkynyl, C₃-C₆ haloalkynyl,C₂-C₆ alkoxyalkyl, C₂-C₆ alkylthioalkyl, C₁-C₆ nitroalkyl, C₂-C₆cyanoalkyl, C₃-C₈ alkoxycarbonylalkyl, C₃-C₆ cycloalkyl, C₃-C₆halocycloalkyl, halogen, CN, SCN, NO₂, OR¹⁷, SR¹⁷, S(O)₂R¹⁷, OC(O)R¹⁷,OS(O)₂R¹⁷, CO₂R¹⁷, C(O)R¹⁷, C(O)NR¹⁷R¹⁸, SO₂NR¹⁷R¹⁸, NR¹⁷R¹⁸, phenyloptionally substituted with 1 to 3 substituents independently selectedfrom W, and benzyl optionally substituted with 1 to 3 substituentsindependently selected from W;

[0081] R³ is selected from the group H, C₁-C₄ alkyl, C₃-C₄alkoxycarbonylalkyl, CO₂R¹⁷, C(O)R¹⁷, phenyl and phenyl substituted by(R¹⁶)_(p);

[0082] R¹⁶ is selected from the group C₁-C₆ alkyl, C₁-C₆ haloalkyl,C₂-C₆ alkenyl, C₂-C₆ haloalkenyl, C₂-C₆ alkynyl, C₃-C₆ haloalkynyl,C₂-C₆ alkoxyalkyl, C₂-C₆ alkylthioalkyl, C₁-C₆ nitroalkyl, C₂-C₆cyanoalkyl, C₃-C₈ alkoxycarbonylalkyl, C₃-C₆ cycloalkyl, C₃-C₆halocycloalkyl, halogen, CN, SCN, NO₂, OR¹⁷, SR¹⁷, S(O)₂R¹⁷, OC(O)R¹⁷,OS(O)₂R¹⁷, CO₂R¹⁷, C(O)R¹⁷, C(O)NR¹⁷R⁸, SO₂NR¹⁷R¹⁸, NR¹⁷R¹⁸, phenyloptionally substituted with 1 to 3 substituents independently selectedfrom W, and benzyl optionally substituted with 1 to 3 substituentsindependently selected from W;

[0083] R¹⁷is selected from the group C₁-C₄ alkyl, C₁-C₂ haloalkyl, C₃-C₄alkenyl and propargyl;

[0084] R¹⁸ is selected from the group H and CH₃;

[0085] m is 1 or 2;

[0086] n is 1 or 2; and

[0087] p is 1 or 2.

[0088] Additional preferred compounds include those wherein

[0089] R^(2′) is NR^(6′)R^(7′);

[0090] R^(3′) is chlorine;

[0091] R^(4′) is CF₃—, CF₃O— or —SF₅;

[0092] R^(5′) is alkyl;

[0093] R^(6′) is hydrogen;

[0094] R^(7′) is hydrogen, —S(O)_(q′)CF₃, or alkyl optionallysubstituted by —S(O)_(s′)R^(8′) or aminocarbonyl;

[0095] X is CR^(13′);

[0096] R^(13′) is chlorine or bromine; and

[0097] m′ is 0 or 1.

[0098] A further particularly preferred class of compounds of generalformula (I) because of their systemic aphicidal properties are thosewherein:

[0099] R^(2′) is NR^(6′)R^(7′);

[0100] R^(3′) is chlorine;

[0101] R^(4′) is CF₃— or —SF₅;

[0102] R^(5′) is methyl or ethyl;

[0103] R^(6′) is hydrogen;

[0104] R^(7′) is hydrogen, methyl or ethyl optionally substituted by—S(O)_(s′)R^(8′) or aminocarbonyl;

[0105] R^(8′) is methyl or ethyl;

[0106] R^(9′) is methyl or ethyl;

[0107] X is CR^(13′);

[0108] R^(13′) is chlorine or bromine; and

[0109] m′ is 0 or 1.

[0110] Additional preferred compounds are those in the following tables:TABLE 1

R¹ R² R³ CF₃ Cl 4-Cl-Ph OCF₃ Cl CO₂Me CF₃ Cl CO₂Me Br Cl CO₂Me Cl ClCO₂Me OCF₃ F 4-F-Ph Cl F 4-F-Ph Br F 4-F-Ph OCF₃ Cl Me Br Cl Me OCF₃ Cln-Pr Br Cl n-Pr Cl Cl n-Pr OCF₃ CF₃ CO₂Me Cl CF₃ CO₂Me CF₃ F CO₂Me Br FCO₂Me Cl F CO₂Me OCF₃ F CO₂Me Br F Ph OCF₃ F Ph CF₃ F 4-F-Ph OCF₃ F EtCF₃ F Et OCF₃ F Me CF₃ F Me OCF₃ Cl CO₂Et CF₃ CF₃ CO₂Me Cl F Me

[0111] TABLE 2

R¹ R² R³ R⁴ Y OCF₃ Cl CO₂Me H Me OCF₃ Cl CO₂Me Me H OCF₃ Cl CO₂Me HCO₂Me OCF₃ Cl CO₂Me H CO₂Me Br F 4-F-Ph H Me Br F 4-F-Ph H CO₂Me Br F4-F-Ph H CO₂Me Br F 4-F-Ph Me H Br F 4-F-Ph Et H OCF₃ Cl CO₂Me Et H CF₃F CO₂Me Me H OCF₃ F CO₂Me Me H OCF₃ F 4-F-Ph Et H OCF₃ F 4-F-Ph Me H BrCl CO₂Me H Me CF₃ Cl CO₂Me H Me CF₃ F CO₂Me Et H CF₃ Cl CO₂Me H CO₂Me BrCl CO₂Me H CO₂Me OCF₃ F CO₂Me H Me CF₃ F CO₂Me H Me OCF₃ Cl CO₂Et H EtOCF₃ Cl CO₂Me H Et CF₃ Cl CO₂Et H Et CF₃ Cl CO₂Me H Et OCF₃ Cl CO₂Me HCO₂Et Br F 4-F-Ph H CO₂Et Br F 4-F-Ph H Et Br F 4-F-Ph H COMe OCF₃ ClCO₂Et H Me OCF₃ F 4-F-Ph H CO₂Et OCF₃ F 4-F-Ph H Et Br F 4-F-Ph H CH₂SMe

[0112] TABLE 3

R¹ R² R³ OCF₃ F 4-F-Ph OCF₃ Cl 4-F-Ph OCF₃ F Me

[0113] TABLE 4

R¹ R² R³ Y OCF₃ Cl Me H CF₃ Cl Me H CF₃ Cl Et H CF₃ F Et H OCF₃ F Et HOCF₃ Cl CO₂Me H CF₃ Cl CO₂Me H Br Cl CO₂Me H Cl Cl CO₂Me H OCF₃ F CO₂MeH CF₃ F CO₂Me H Br F CO₂Me H Cl F CO₂Me H OCF₃ Cl CO₂Me Me CF₃ Cl CO₂MeMe Br Cl CO₂Me Me

[0114] TABLE 5

R¹ R² R³ OCH₃ Cl CO₂CH₃

[0115] TABLE 6

R¹ R² R³ E H H Ph H

[0116] Unless otherwise specified, alkyl and alkoxy groups have from oneto four carbon atoms. The haloalkyl and haloalkoxy groups likewisepreferably have one to four carbon atoms. The various individualaliphatic hydrocarbon moieties, that is, radicals and portions thereof(for example the alkyl moiety of alkylaminocarbonyl andalkylaminosulfonyl), have up to four carbon atoms in the chain.

[0117] The haloalkyl and haloalkoxy groups can bear one or more halogenatoms.

[0118] The term heteroaryl refers to a five to seven memberedheterocyclic ring containing from one to four heteroatoms selected fromnitrogen, oxygen and sulfur.

[0119] In the above definitions, the term “alkyl” used either alone orin compounds words such as “alkylthio” or “haloalkyl,” denotes straightchain or branched alkyl, such as methyl, ethyl, n-propyl, isopropyl orthe different butyl, pentyl, hexyl isomers. Alkoxy denotes methoxy,ethoxy, n-propyloxy, isopropyloxy and the different butoxy or pentoxyisomers. Alkenyl denotes straight chain or branched alkenes, such asvinyl, 1-propenyl, 2-propenyl, 3-propenyl and the different butenyl,pentenyl and hexenyl isomers. Alkynyl denotes straight chain or branchedalkynes, such as ethynyl, 1-propynyl, 3-propynyl and the differentbutynyl, pentynyl and hexynyl isomers. Alkylthio denotes methylthio,ethylthio and the different propylthio, butylthio, pentylthio andhexylthio isomers. Alkylsulfinyl, alkylsulfonyl, alkylamino, and thelike are defined analogously to the above examples. Cycloalkyl denotescyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

[0120] The term “halogen,” either alone or in compound words such as“haloalkyl,” denotes fluorine, chlorine, bromine or iodine. Further,when used in compound words such as “haloalkyl,” said alkyl may bepartially or fully substituted with halogen atoms, which may be the sameor different. Examples of haloalkyl include CH₂CH₂F, CF₂CF₂ andCH₂CHFCl. The terms “halocycloalkyl,” “haloalkenyl” and “haloalkynyl”are defined analogously to the term “haloalkyl”.

[0121] The total number of carbon atoms in a substituent group isindicated by the “C_(i)-C_(j)” prefix where I and j are numbers from 1to 8. For example, C₁-C₃ alkylsulfonyl designates methylsulfonyl throughpropylsulfonyl; C₂ alkoxyalkoxy designates OCH₂OCH₃; C₄ alkoxyalkoxydesignates the various isomers of an alkoxy group substituted with asecond alkoxy group containing a total of 4 carbon atoms, examplesincluding OCH₂OCH₂CH₂CH₃ and OCH₂CH₂OCH₂CH₃; C₂ cyanoalkyl designatesCH₂CN and C₃ cyanoalkyl designates CH₂CH₂CN and CH(CN)CH₃; C₂alkylcarbonyl designates C(O)CH₃ and C₄ alkylcarbonyl includesC(O)CH₂CH₂CH₃ and C(O)CH(CH₃)₂; C₂ alkoxycarbonyl designates C(O)OCH₃and C₄ alkoxycarbonyl designates C(O)OCH₂CH₂CH₃ and C(O)OCH(CH₃)₂; andas a final example, C₃ alkoxycarbonylalkyl designates CH₂CO₂CH₃ and C₄alkoxycarbonylalkyl includes CH₂CH₂CO₂CH₃, CH₂CO₂CH₂CH₃ andCH(CH₃)CO₂CH₃.

[0122] Preferably, the compounds are indoxacarb and ethiprole. In apreferred embodiment, the compositions and methods are used for treatingrice crops. Various insects can be controlled using the compositionsdescribed herein by applying an effective amount of the compositions tothe plants or to the medium in which they grow.

DETAILED DESCRIPTION OF THE INVENTION

[0123] The present invention is directed to compositions and methods forcontrolling insect populations. The compositions include one or morecompounds from Formula 1A and one or more compounds from Formulas 1B-Gdescribed above, where the compounds preferably include indoxacarb andethiprole, in at least an amount effective to control populations ofNilaparvata lugens (brown planthoppers), Cnaphalocrocis medinalis (riceleaf rollers) and Nephotettix spp. (rice leaf hoppers), for example,Nephotettix cincticeps (green leaf hopper), when applied to rice crops.In some embodiments, a synergistic effect is observed between theindoxacarb and the ethiprole with respect to their ability to controlpopulations of Nephotettix spp. Synergy tends to be observed when thecomposition is applied to the insects as well as the plants. Synergydoes not tend to be observed when the composition is applied only to theplants and then untreated insects are introduced to the treated plants.

[0124] I. Insecticidal Compositions

[0125] The compositions include one or more compounds of Formula 1A andone or more compounds of Formulas 1B-G. The compounds are preferablyindoxacarb and ethiprole, and are preferably present in an amount whichprovides for synergistic effects with respect to controlling Nephotettixcincticeps (green leaf hopper). When used in connection with theprotection of rice crops from insect infestation, the compositions areadvantageous in that they allow application of a single composition tocontrol all of the major insects which attack rice crops, namely,Nilaparvata lugens (brown planthoppers), Cnaphalocrocis medinalis (riceleaf rollers) and Nephotettix spp. (rice leaf hoppers), for example,Nephotettix cincticeps (green leaf hopper).

[0126] The compositions usually contain from 0.00005% to 90%, morepreferably from 0.001% to 40% by weight of total active ingredients, andoptionally include other insecticides, suitable carriers, anthelmintics,anticoccidials, synergists, trace elements, stabilizers, and othercomponents commonly found in insecticidal compositions.

[0127] The actual compositions employed and their rate of applicationwill be selected to achieve the desired effect(s) by the farmer,livestock producer, medical or veterinary practitioner, pest controloperator other person skilled in the art. Solid and liquid compositionsfor application topically to animals, timber, stored products orhousehold goods preferably contain from 0.00005% to 90%, more preferablyfrom 0.001% to 40%, by weight of the active compounds.

[0128] Dusts and liquid compositions for application to livestock,persons, goods, premises or outdoor areas may contain 0.00005% to 90%,and more preferably 0.001% to 40%, by weight of the active compounds,which are preferably ethiprole and indoxacarb.

[0129] The compositions can be used to control pests which feed on partsof the plant remote from the point of application, e.g., leaf feedinginsects can be killed by the subject compounds applied to roots.Alternatively, the compounds can be applied by foliar application. Inone embodiment, ethiprole and/or related compounds are applied to theroots, and indoxacarb or related compounds are applied as a foliarspray. In addition, the compounds may reduce attacks on the plant bymeans of antifeeding or repellent effects.

[0130] A. Indoxacarb

[0131] Indoxacarb by itself is not particularly active againstNilaparvata lugens (brown planthoppers), but is very active againstCnaphalocrocis medinalis (rice leaf rollers). It has some activity byitself against Nephotettix cincticeps (green leaf hoppers), but theactivity tends to be slow. The activity of indoxacarb againstNephotettix cincticeps ( tends to be speeded up by the addition ofethiprole. Further, the overall toxicity of indoxacarb tends to beincreased by the addition of ethiprole. The chemical formula forindoxacarb is:

[0132] B. Ethiprole

[0133] Ethiprole is not particularly active against Cnaphalocrocismedinalis (rice leaf rollers), but shows activity against Nilaparvatalugens (brown planthoppers). It has some activity by itself againstNephotettix cincticeps (green leaf hoppers). The chemical formula forethiprole is:

[0134] With respect to controlling populations of Nephotettix cincticeps(green leaf hoppers), synergy is observed when the ethiprole andindoxacarb were applied in ratios of between 2:1 and 32:1 by weight.This effect is surprising, since neither ethiprole nor indoxacarb areparticularly effective alone at controlling this type of insect.

[0135] C. Other Insecticides

[0136] The compositions can include other insecticides in addition tothe compounds of Formulas 1A-G, which are preferably ethiprole andindoxacarb. Suitable insecticides include fipronil, acephate,chlorpyrifos, demeton-S-methyl, disulfoton, ethoprofos, fenitrothion,malathion, monocrotophos, parathion, phosalone, pirimiphos-methyl,triazophos, cyfluthrin, cypermethrin, deltamethrin, fenpropathrin,fenvalerate, permethrin, aldicarb, carbosulfan, methomyl, oxamyl,pirimicarb, bendiocarb, teflubenzuron, dicofol, endosulfan, lindane,benzoximate, cartap, cyhexatin, tetradifon, avermectins, ivermectin,milbemycins, thiophanate, trichlorfon, dichlorvos, diaveridine, spinosadand dimetridazole, although those of skill in the art are aware ofnumerous other useful insecticides.

[0137] D. Optional Additional Components

[0138] The compositions may include, if appropriate, suitable carriers,anthelmintics, anticoccidials, synergists, trace elements, stabilisers,adhesives, wetting agents, dispersants, emulsifiers, penetrants,solvents, fillers and/or carriers which are conventional in each case.

[0139] Compositions in the form of aerosols and aqueous or non-aqueoussolutions or dispersions suitable for spraying, fogging and low- orultra-low volume spraying may be used. Suitable solid diluents which maybe used in the preparation of compositions suitable for applying thecompositions include aluminum silicate, kieselguhr, corn husks,tricalcium phosphate, powdered cork, absorbent carbon black, magnesiumsilicate, a clay such as kaolin, bentonite or attapulgite, and watersoluble polymers and such solid compositions may, if desired, containone or more compatible wetting, dispersing, emulsifying or colouringagents which, when solid, may also serve as diluent.

[0140] Such solid compositions, which may take the form of dusts,granules or wettable powders, are generally prepared by impregnating thesolid diluents with solutions of the compositions in volatile solvents,evaporating the solvents and, if necessary, grinding the products so asto obtain powders and, if desired, granulating or compacting theproducts so as to obtain granules, pellets or briquettes or byencapsulating finely divided active ingredient in natural or syntheticpolymers, e.g., gelatin, synthetic resins and polyamides.

[0141] The wetting, dispersing and emulsifying agents which may bepresent, particularly in wettable powders, may be of the ionic ornon-ionic types, for example sulphoricinoleates, quaternary ammoniumderivatives or products based upon condensates of ethylene oxide withnonyl- and octylphenol, or carboxylic acid esters of anhydrosorbitolswhich have been rendered soluble by etherification of the free hydroxygroups by condensation with ethylene oxide, or mixtures of these typesof agents. Wettable powders may be treated with water immediately beforeuse to give suspensions ready for application.

[0142] Liquid compositions for the application of the compositions maytake the form of solutions, suspensions and emulsions of thecompositions optionally encapsulated in natural or synthetic polymers,and may, if desired, incorporate wetting, dispersing or emulsifyingagents. These emulsions, suspensions and solutions may be prepared usingaqueous, organic or aqueous-organic diluents, for example acetophenone,isophorone, toluene, xylene, mineral, animal or vegetable oils, andwater soluble polymers (and mixtures of these diluents), which maycontain wetting, dispersing or emulsifying agents of the ionic ornon-ionic types or mixtures thereof, for example those of the typesdescribed above. When desired, the emulsions containing the compositionsmay be used in the form of self-emulsifying concentrates containing theactive substance dissolved in the emulsifying agents or in solventscontaining emulsifying agents compatible with the active substance, thesimple addition of water to such concentrates producing compositionsready for use.

[0143] The compositions, when applied to control arthropod, plantnematode, helminth or protozoan pests, may also contain synergists (e.g.piperonyl butoxide or sesamex), stabilizing substances, otherinsecticides, acaricides, plant nematocides, anthelmintics oranticoccidials, fungicides (agricultural or veterinary as appropriatee.g. benomyl, iprodione), bactericides, arthropod or vertebrateattractants or repellents or pheromones, reodorants, flavoring agents,dyes and auxiliary therapeutic agents, e.g., trace elements. These maybe designed to improve potency, persistence, safety, uptake wheredesired, spectrum of pests controlled or to enable the composition toperform other useful functions in the same animal or area treated.

[0144] E. Formulations Including the Compositions Described Herein

[0145] The mixing ratios of the ethiprole and indoxacarb can vary withinwide limits, depending on numerous factors, including the relativepopulations of the insects to be controlled. However, it is preferredthat the ethiprole and indoxacarb are present in an amount whichprovides for a synergistic effect with respect to controllingNephotettix spp. The compositions can also include suitable formulationauxiliaries.

[0146] The compositions can exist not only as mixed formulations of thetwo components which are then diluted with water in the customary manneror applied as granules, but also in the form of so-called tank mixes byjointly diluting the components, which are formulated separately, withwater.

[0147] Based on these formulations, it is also possible to preparecombinations with other pesticidally active substances, such asselective herbicides and specific fungicides or insecticides, and alsofertilizers and/or growth regulators, for example in the form of areadymix or a tank mix.

[0148] The components can be formulated in a variety of ways. Suitableformulation options are, for example: yeast formulations, starchformulations, wettable powders (WP), emulsifiable concentrates (EC),aqueous solutions (SL), emulsions (EW) such as oil-in-water andwater-in-oil emulsions, sprayable solutions or emulsions, oil- orwater-based dispersions, suspoemulsions, dusts (DP), seed treatmentproducts, granules for soil or paddy application or spreading, orwater-dispersible granules (WG), ULV formulations, microcapsules orbaits (substrates). Oil-in-water and water-in-oil emulsions, wettablepowders or granules are of particular interest.

[0149] These individual formulation types are known in principle and aredescribed, for example, in: Winnacker-Kuchler, “Chemische Technologie”Chemical Technology, Vol. 7, C. Hauser Verlag Munich, 4th Ed. 1986; vanValkenburg, “Pesticide Formulations”, Marcel Dekker N.Y., 2nd Edition1972-73; K. Martens, “Spray Drying Handbook”, 3rd Edition, G. GoodwinLtd. London.

[0150] The formulation auxiliaries required, such as inert materials,surfactants, solvents and other additives, are also known and aredescribed, for example, in: Watkins, Handbook of Insecticide DustDiluents and Carriers, 2nd Edition, Darland Books, Caldwell N.J.; H. V.Olphen, Introduction to Clay Colloid Chemistry, 2nd Edition, J. Wiley &Sons, N.Y., Marsden, Solvents Guide, 2nd Edition, Interscience, N.Y.1950; McCutcheon's, “Detergents and Emulsifiers Annual”, MC Publ. Corp.,Ridgewood N.J.; Sisley and Wood, “Encyclopedia of Surface ActiveAgents”, Chem. Publ. Co. Inc., N.Y. 1964; Schonfeldt,“Grenzflachenaktive Athylenoxidaddukte” Surface-active Ethylene OxideAdducts, Wiss. Verlagsgesell., Stuttgart 1976; Winnacker-Kuchler,“Chemische Technologie” Chemical Technology, Vol. 7, C. Hauser VerlagMunich, 4th Ed. 1986.

[0151] Wettable powders are preparations which are uniformly dispersiblein water and which, besides the active substance, also comprise wettingagents, for example polyoxyethylated alkylphenols, polyoxyethylatedfatty alcohols or fatty amines, alkane sulfonates or alkylbenzenesulfonates, and dispersants, for example sodium lignosulfonate, sodium2,2′-dinaphthylmethane-6,6′-disulfonate, sodium dibutylnaphthalenesulfonate, or else sodium oleoylmethyltaurinate, in addition to adiluent or inert substance.

[0152] Emulsifiable concentrates can be prepared by dissolving theactive substance in an organic solvent, for example butanol,cyclohexanone, dimethylformamide, xylene, or else higher-boilingaromatic compounds or hydrocarbons, with the addition of one or moreemulsifiers. Examples of emulsifiers which can be used are: calciumalkylarylsulfonates, such as calcium dodecylbenzenesulfonate, ornon-ionic emulsifiers, such as fatty acid polyglycol esters, alkylarylpolyglycol ethers, fatty alcohol polyglycol ethers, propyleneoxide/ethylene oxide condensates, alkyl polyethers, sorbitan fatty acidesters, polyoxyethylene sorbitan fatty acid esters or polyoxyethylenesorbitol esters.

[0153] Dusts can be obtained by grinding the active substance withfinely divided solid substances, for example talc, natural clays, suchas kaolin, bentonite and pyrophyllite, or diatomaceous earth. Granulescan be produced either by spraying the active substance onto adsorptive,granulated inert material or by applying active substance concentratesto the surface of carriers, such as sand, kaolinites or granulated inertmaterial, by means of binders, for example polyvinyl alcohol, sodiumpolyacrylate or, alternatively, mineral oils. Suitable active substancescan also be granulated in the manner which is conventional for theproduction of fertilizer granules, if desired in a mixture withfertilizers.

[0154] As a rule, the agrochemical preparations comprise 0.0001 to 99percent by weight, in particular between 0.0005 and 95%, particularlypreferably between 2 and 90%, of the active components, for example,ethiprole and indoxacarb.

[0155] The concentration of active substance in wettable powders is, forexample, about 10 to 90% by weight; the remainder to 100% by weight iscomposed of conventional formulation components. In the case ofemulsifiable concentrates, the concentration of active substance can beabout 1 to 90% by weight, preferably 5 to 80% by weight. Formulations inthe form of dusts comprise about 1 to 30% by weight, preferably 5 to 20%by weight, of active substance, sprayable solutions about 0.05 to 80% byweight, preferably 2 to 50% by weight, of active substance. In the caseof granules, for example water-dispersible granules, the activesubstance content depends partly on whether the active compound is inliquid or solid form and on which granulation auxiliaries and fillersare used. As a rule, water-dispersible granules comprise between 1 and95% by weight, granules for spreading between 1 and 50%, preferablybetween 2 and 25%. Baits have an active substance content of between0.0001 and 10% as regards the active compounds, for example, ethiproleand indoxacarb. The use concentration can vary between 0.1 ppm (0.0001g/l) and 10,000 ppm ( 10 g/l), preferably between 0.5 and 5,000 ppm,particularly preferably between 5 and 1,000 ppm.

[0156] II. Insects which can be Treated

[0157] Preferably, the compositions are used to treat rice crops forpests such as Nilaparvata lugens (brown planthoppers), Cnaphalocrocismedinalis (rice leaf rollers), and Nephotetlix spp. (rice leaf hoppers),for example, Nephotettix cincticeps (green leaf hopper) the most commonpests to attack rice crops.

[0158] The compositions described herein can generally be used tocontrol arthropod, plant nematode, helminth or protozoan pests at alocus by treating the locus (for example, by application oradministration) with an effective amount of the compositions. Thecompositions may, in particular, be used in the field of veterinarymedicine and livestock husbandry and in the maintenance of public healthagainst arthropods, helminths or protozoa which are parasitic internallyor externally upon vertebrates, particularly warm-blooded vertebrates,for example man and domestic animals, e.g. cattle, sheep, goats,equines, swine, poultry, dogs, cats and fishes, for example Acarina,including fleas, ticks (e.g. Ixodes spp., Boophilus spp. e.g. Boophilusmicroplus, Amblyomma spp., Hyalomma spp., Rhipicephalus spp. e.g.Rhipicephalus appendiculatus, Haemaphysalis spp., Dermacentor spp.,Ornithodorus spp. (e.g. Ornithodorus moubata and mites (e.g. Damaliniaspp., Dermahyssus gallinae, Sarcoptes spp. e.g. Sarcoptes scabiei,Psoroptes spp., Chorioptes spp., Demodex spp., Eutrombicula spp.);Diptera (e.g. Aedes spp., Anopheles spp., Musca spp., Hypoderma spp.,Gasterophilus spp., Simulium spp.); Hemiptera (e.g. Triatoma spp.);Phthiraptera (e.g. Damalinia spp., Linognathus spp.); Siphonapters (e.g.Ctenocephalides spp.); Dictyoptera (e.g. Periplaneta spp., Blatellaspp.); Hymenoptera (e.g. Monomorium pharaonis); for example againstinfections of the gastro-intestinal tract caused by parasitic nematodeworms, for example members of the family Trichostrongylidae,Nippostrongylus brasiliensis, Trichinella spiralis, Haemonchuscontortus, Trichostrongylus colubriformis, Nematodirus battus,Ostertagia circumcincta, Trichostrongylus axei, Cooperia spp. andHymenolepis nana; in the control and treatment of protozoal diseasescaused by, for example, Eimeria spp. e.g. Eimeria tenella, Eimeriaacervulina, Eimeria brunetti, Eimeria maxima and Eimeria necatrix,Trypanosoma cruzi, Leishmania spp., Plasmodium spp., Babesia spp.,Trichomonadidae spp., Histomonas spp., Giardia spp., Toxoplasma spp.,Entamoeba histolytica and Theileria spp.; in the protection of storedproducts, for example cereals, including grain and flour, groundnuts,animal feedstuffs, timber and household goods, e.g. carpets andtextiles, against attack by arthropods, more especially beetles,including weevils, moths and mites, for example Ephestia spp. (flourmoths), Anthrenus spp. (carpet beetles), Tribolium spp. (flour beetles),Sitophilus spp. (grain weevils) and Acarus spp. (mites), to controlcockroaches, silverfish, spiders, ants and termites and similararthropod pests in infested domestic and industrial premises and in thecontrol of mosquito larvae in waterways, wells, reservoirs or otherrunning or standing water; for the treatment of foundations, structureand soil in the prevention of the attack on buildings by termites, forexample, Reticulitermes spp., Heterotermes spp., Coptotermes spp.; inagriculture, against adults, larvae and eggs of Lepidoptera (butterfliesand moths), e.g. Heliothis spp. such as Heliothis virescens (tobaccobudworm), Heliothis armigera and Heliothis zea, Spodoptera spp. such asS. exempta, S. littoralis (Egyptian cotton worm), S. eridania (southernarmy worm), Mamestra configurata (bertha army worm); Earias spp. e.g. E.insulana (Egyptian bollworm), Pectinochora spp. e.g. Pectinophoragossypiella (pink bollworm), Ostrinia spp. such as O. nubilalis(European cornborer), Trichoplusia ni (cabbage looper), Pieris spp.(cabbage worms), Laphygma spp. (army worms), Agrotis and Amathes spp.(cutworms), Wiseana spp. (porina moth), Chilo spp. (rice stem borer),Tryporyza spp. and Diatraea spp. (sugar cane borers and rice borers),Sparganothis pilleriana (grape berry moth), Cydia pomonella (codlingmoth), Archips spp. (fruit tree tortrix moths), Plutella xylostella(diamond back moth); against adult and larvae of Coleoptera (beetles)e.g. Hypothenemus hampei (coffee berry borer), Hylesinus spp. (barkbeetles), Anthonomus grandis (cotton boll weevil), Acalymma spp.(cucumber beetles), Lema spp., Psylliodes spp., Leptinotarsadecemlineata (Colorado potato beetle), Diabrotica spp. (corn rootworms),Gonocephalum spp. (false wire worms) Agriotes spp. (wireworms),Dermolepida and Heteronychus spp. (white grubs), Phaedon cochleariae(mustard beetle), Lissorhoptrus oryzophilus (rice water weevil),Meligethes spp. (pollen beetles), Ceutorhynchus spp., Rhynchophorus andCosmopolites spp. (root weevils); against Hemiptera e.g. Psylla spp.,Bemisia spp., Trialeurodes spp., Aphis spp., Myzus spp., Megoura viciae,Phylloxera spp., Adelges spp., Phorodon humuli (hop damson aphid),Aeneolamia spp., Nephotettix spp. (rice leaf hoppers), Empoasca spp.,Nilaparvata spp., Perkinsiella spp., Pyrilla spp., Aonidiella spp. (redscales), Coccus spp., Pseucoccus spp., Helopeltis spp. (mosquito bugs),Lygus spp., Dysdercus spp., Oxycarenus spp., Nezara spp.; Hymenopterae.g. Athalia spp. and Cephus spp. (saw flies), Atta spp. (leaf cuttingants); Diptera e.g. Hylemyia spp. (root flies), Atherigona spp. andChlorops spp. (shoot flies), Phytomyza spp. (leaf miners), Ceratitisspp. (fruit flies); Thysanoptera such as Thrips tabaci; Orthoptera suchas Locusta and Schistocerca spp. (locusts) and crickets e.g. Gryllusspp. and Acheta spp.; Collembola e.g. Sminthurus spp. and Onychiurusspp. (springtails), Isoptera e.g. Odontotermes spp. (termites),Dernaptera e.g. Forficula spp. (earwigs) and also other arthropods ofagricultural significance such as Acari (mites) e.g. Tetranychus spp.,Panonychus spp. and Bryobia spp. (spider mites), Eriophyes spp. (gallmites), Polyphacotarsonemus spp.; Blaniulus spp. (millipedes),Scutigerella spp. (symphilids), Oniscus spp. (woodlice) and Triops spp.(crustacea); nematodes which attack plants and trees of importance toagriculture, forestry and horticulture either directly or by spreadingbacterial, viral, mycoplasma or fungal diseases of the plants, root-knotnematodes such as Meloidogyne spp. (e.g. M. incognita); cyst nematodessuch as Globodera spp. (e.g. G. rostochiensis); Heterodera spp. (e.g. H.avenae); Radopholus spp. (e.g. R. similis); lesion nematodes such asPratylenchus spp. (e.g. P. pratensis); Belonolaimus spp. (e.g. B.gracilis); Tylenchulus spp. (e.g. T. semipenetrans); Rotylenchulus spp.(e.g. R. reniformis); Rotylenchus spp. (e.g. R. robustus);Helicotylenchus spp. (e.g. H. multicinctus); Hemicycliophora spp. (e.g.H. gracilis); Criconemoides spp. (e.g. C. similis); Trichodorus spp.(e.g. T. primitivus); dagger nematodes such as Xiphinema spp. (e.g. X.diversicaudatum), Longidorus spp. (e.g. L. elongatus); Hoplolaimus spp.(e.g. H. coronatus); Aphelenchoides spp. (e.g. A. ritzemabosi, A.besseyi); stem and bulb eelworms such as Ditylenchus spp. (e.g. D.dipsaci).

[0159] The compositions can also be used to treat humans infected with,for example, Head lice (Pediculus humanus capitis) and body lice(Pediculus humanus humanus).

[0160] III. Plant Varieties which can be Protected Using theCompositions Described Herein

[0161] The compositions can be used to protect cereal crops (such asmaize, wheat, rice, sorghum), in particular rice crops, and can also beused in connection with field, forage, plantation, glasshouse, orchardand vineyard crops, of ornamentals and of plantation and forest trees,for example, cotton, tobacco, vegetables and salads (such as beans, colecrops, curcurbits, lettuce, onions, tomatoes and peppers), field crops(such as potato, sugar beet, ground nuts, soyabean, oil seed rape),sugar cane, grassland and forage (such as maize, sorghum, lucerne),plantations (such as of tea, coffee, cocoa, banana, oil palm, coconut,rubber, spices), orchards and groves (such as of stone and pip fruit,citrus, kiwifruit, avocado, mango, olives and walnuts), vineyards,ornamental plants, flowers and shrubs under glass and in gardens andparks, forest trees (both deciduous and evergreen) in forests,plantations and nurseries.

[0162] The compositions can also be used to protect timber (standing,felled, converted, stored or structural) from attack by sawflies (e.g.Urocerus) or beetles (e.g. scolytids, platypodids, lyctids, bostrychids,cerambycids, anobiids), or termites, for example, Reticulitermes spp.,Heterotermes spp., Coptotermes spp.

[0163] The compositions can also be used to protect stored products suchas grains, fruits, nuts, spices and tobacco, whether whole, milled orcompounded into products, from moth, beetle and mite attack. Alsoprotected are stored animal products such as skins, hair, wool andfeathers in natural or converted form (e.g. as carpets or textiles) frommoth and beetle attack; also stored meat and fish from beetle, mite andfly attack.

[0164] IV. Methods of Controlling Insects

[0165] To control arthropods and nematodes, the compositions aregenerally applied to the locus in which arthropod or nematodeinfestation is to be controlled at a rate of about 0.00001 kg to about20 kg per hectare of locus treated. Under ideal conditions, depending onthe pest to be controlled, the lower rate may offer adequate protection.On the other hand, adverse weather conditions, resistance of the pestand other factors may require that the active ingredient be used inhigher proportions. In foliar application, a rate of 0.0001 g/ha to 1000g/ha may be used.

[0166] When the pest is soil-borne, the composition is distributedevenly over the area to be treated in any convenient manner. Applicationmay be made, if desired, to the field or crop-growing area generally orin close proximity to the seed or plant to be protected from attack. Theactive component can be washed into the soil by spraying with water overthe area or can be left to the natural action of rainfall. During orafter application, the formulation can, if desired, be distributedmechanically in the soil, for example by ploughing or disking.Application can be prior to planting, at planting, after planting butbefore sprouting has taken place or after sprouting.

[0167] The composition may be applied in solid or liquid compositions tothe soil principally to control those nematodes dwelling therein butalso to the foliage principally to control those nematodes attacking theaerial parts of the plants (e.g. Aphelenchoides spp. and Ditylenchusspp. listed above).

[0168] Suitable means of applying the compositions to growing cropsinclude foliar sprays, dusts, granules, fogs and foams; also assuspensions of finely divided particles; as soil and root treatments byliquid drenches, dusts, granules, smokes and foams; and as seeddressings by liquid slurries and dusts.

[0169] Among the cultivated plants, the methods described herein aremost particularly effective in rice plants cultivated in a paddy field.

[0170] As will be well understood to those of skill in the art, theapplication rate of the composition will be expected to vary with theexternal conditions, for example, temperature, humidity and the like, aswell as the particular field of application and on the plant to betreated. Accordingly, it can vary within wide limits.

[0171] The two major components, which are the at least one compoundfrom Formula 1A and at least one compound from Formulas 1B-G, and whichare preferably ethiprole and indoxacarb, can be applied simultaneouslyor in succession. However, for ease of application, it is preferred thatthe composition which is applied to the plants include both components.

[0172] The present invention will be better understood with reference tothe following non-limiting examples.

EXAMPLE 1 Activity of the Compositions Against Nephotettix cincticeps(Green Leaf Hopper), Nilaparvata lugens (Brown Planthoppers) andCnaphalocrocis medinalis (Rice Leaf Rollers)

[0173] In experiments on activity against Nephotettix spp. (rice leafhoppers), for example, Nephotettix cincticeps (green leaf hopper),carried out on representative compounds of the first preferredembodiment, the following results (wherein ppm indicates theconcentration of the compound in parts per million of the test solutionapplied) have been obtained, as shown in Table 7: TABLE 7 Nephotettixcincticeps Results % mortality Indoxacarb (ppm) 0 6.25 12.5 25 Ethiprole0 0.0 0.0 16.2 38.0 (ppm) 200 0.0 37.8 66.2 96.0

[0174] As shown in the table, Indoxacarb at 25 ppm results in a 38%kill, and Ethiprole at 200 ppm results in a 37.8% kill. The combinationprovides significantly more kill (96.0%) wthan either Ethiprole orIndoxacarb alone.

We claim:
 1. An insecticidal composition which comprises synergisticallyinsecticidal effective amounts of one or more compounds of the followingFormula 1A and one or more compounds of the following Formulas 1B-G:

wherein: E is selected from the group H and C₁-C₃ alkyl; or Y isselected from the group H; C₁-C₆ alkyl, benzyl; C₂-C₆ alkoxyalkyl; C₂-C₆alkenyl; C₂-C₆ alkynyl; C₁-C₆ alkyl optionally substituted by halogen,C₁-C₃ alkoxy, C₁-C₃ haloalkoxy, —CN, —NO₂, —S(O)_(r)R³², —COR³²,—CO₂R³², phenyl optionally substituted by halogen, —CN, —C₁-C₂ haloalkyland/or C₁-C₂ haloalkoxy; C₃-C₆ cycloalkyl; C₃-C₆ cyclohaloalkyl; C₃-C₆cycloalkylalkyl; —CHO; —C₂-C₆ alkylcarbonyl; —C₂-C₆ alkoxycarbonyl;—C₂-C₆ haloalkylcarbonyl; —COR³⁶; —CO₂R³⁶; —C₁-C₆ alkylthio; —C₁-C₆haloalkylthio; phenylthio; R¹²OC(O)N(R¹³)S— and R¹⁴ (R¹⁵)NS—; R¹ and R²are independently selected from the group H, C₁-C₆ alkyl, C₁-C₆haloalkyl, C₂-C₆ alkenyl, C₂-C₆ haloalkenyl, C₂-C₆ alkynyl, C₃-C₆haloalkynyl, C₂-C₆ alkoxyalkyl, C₂-C₆ alkylthioalkyl, C₁-C₆ nitroalkyl,C₂-C₆ cyanoalkyl, C₃-C₈ alkoxycarbonylalkyl, C₃-C₆ cycloalkyl, C₃-C₆halocycloalkyl, halogen, —CN, —N₃, —SCN, —NO₂, —OR, —SR¹⁷, —S(O)R¹⁷,—S(O)₂R¹⁷, —OC(O)R¹⁷, —OS(O)₂R¹⁷, —CO₂R¹⁷, —C(O)R¹⁷, —C(O)NR¹⁷R¹⁸,—SO₂NR¹⁷R¹⁸, —NR¹⁷R¹⁸, —NR¹⁸C(O)R¹⁷, —OC(O)NHR¹⁷, —NR¹⁸C(O)NHR¹⁷,—NR¹⁸SO₂R¹⁷, phenyl optionally substituted with 1 to 3 substituentsindependently selected from W, and benzyl optionally substituted with 1to 3 substituents independently selected from W; or when m or n is 2,(R¹)₂ can be taken together, or (R²)₂ can be taken together as —OCH₂O—,—OCF₂O—, —OCH₂CH₂O—, —CH₂C(CH₃)₂O—, —CF₂CF₂O or —OCF₂CF₂O— to form acyclic bridge; provided that when R¹ or R² is —S(O)R¹⁷, —S(O)₂R¹⁷,—OC(O)R¹⁷ or —OS(O)₂R¹⁷ then R¹⁷ is other than H; R³is selected from thegroup H, J, —N₃, —NO₂, halogen, —N(²²)R²³, —C(R³⁴)═N—O—R³⁵, C₁-C₆ alkyl,C₁-C₆ haloalkyl, C₂-C₆ alkenyl, C₂-C₆ haloalkenyl, C₂-C₆ alkynyl, C₂-C₆alkoxylalkyl, C₃-C₈ alkoxycarbonylalkyl, —CO₂R¹⁷, —OR¹⁹, —C(O)R¹⁷,—C(O)NR¹⁷R¹⁸, —C(S)NR¹⁷R¹⁸, —C(S)R¹⁷, —C(S)SR¹⁷, —CN, —Si(²⁸)(R²⁹)R²⁷,—SR²⁷, —S(O)R²⁷, —SO₂R²⁷, —P(O)(OR²⁷)₂, phenyl, phenyl substituted with(R¹⁶)_(p), benzyl and benzyl substituted with 1 to 3 substituentsindependently selected from W; or R³ is —C₂-C₆ epoxyalkyl optionallysubstituted with a group selected from —C₁-C₃ alkyl, —CN, —C(O)R²⁴,—CO₂R²⁴ and phenyl optionally substituted with W; or R³ is C₁-C₆ alkylsubstituted with a group selected from —C(O)N(R²⁵)R²⁶, C(O)R²⁵, —SR²⁷,—S(O)R²⁷, —SO₂R²⁷, —SCN, —CN, —C₁-C₂ haloalkoxy, —Si(R²⁸)R²⁹)R³⁰,—N(²²)R²³, —NO₂—OC(O)R²⁵—P(O)(OR )₂ and J; J is selected from the groupsaturated, partially unsaturated or aromatic 5- or 6-memberedheterocyclic rings, bonded through carbon or nitrogen, containing 1-4heteroatoms independently selected from the group consisting of 0-2oxygen, 0-2 sulfur and 0-4 nitrogen, this substituent optionallycontaining one carbonyl and optionally substituted with one or moremembers selected from W; R⁴ is selected from the group H, C₁-C₄ alkyl,—COR²⁰ and C₂-C₄ alkoxycarbonyl; or R¹² is C₁-C₆ alkyl; R¹³ is C₁-C₄alkyl; R¹⁴ and R¹⁵ are independently C₁-C₄ alkyl; or R¹⁴ and R¹⁵ can betaken together as —CH₂CH₂CH₂CH₂CH₂— or —CH₂CH₂OCH₂CH₂—; R¹⁶ is selectedfrom the group C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₂-C₆ alkenyl, C₂-C₆haloalkenyl, C₂-C₆ alkynyl, C₃-C₆ haloalkynyl, C₂-C₆ alkoxyalkyl, C₂-C₆alkylthioalkyl, C₁-C₆ nitroalkyl, C₂-C₆ cyanoalkyl, C₃-C₈alkoxycarbonylalkyl, C₃-C₆ cycloalkyl, C₃-C₆ halocycloalkyl, halogen,—CN, —N₃, —SCN, —NO₂, —OR¹⁷, —SR¹⁷, —S(O)R¹⁷, —S(O)₂R¹⁷, —OC(O)R¹⁷,—OS(O)₂R¹⁷, —CO₂R¹⁷, —C(O)R¹⁷, —C(O)NR¹⁷R¹⁸, —SO₂NR¹⁷R¹⁸, —NR¹⁷R¹⁸,—NR¹⁸C(O)R¹⁷, —OC(O)NHR¹⁷, NR¹⁸C(O)NHR¹⁷, —NR¹⁸SO₂R¹⁷, phenyl optionallysubstituted with 1 to 3 substituents independently selected from W, andbenzyl optionally substituted with 1 to 3 substituents independentlyselected from W; or when p is 2, (R¹⁶)₂ can be taken together as—OCH₂O—, —OCF₂O—, —OCH₂CH₂O—, —CH₂C(CH₃)₂O—, —CF₂CF₂O or —OCF₂CF₂O— toform a cyclic bridge; provided that when R¹⁶ is —S(O)R¹⁷, —S(O)₂R¹⁷,—OC(O)R¹⁷ or —OS(O)₂R¹⁷ then R¹⁷ is other than H; R¹⁷ is selected fromthe group H, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₂-C₆ alkenyl, C₂-C₆haloalkenyl, C₂-C₆ alkynyl, C₃-C₆ haloalkynyl, C₂-C₆ alkoxyalkyl, C₂-C₆alkylthioalkyl, C₁-C₆ nitroalkyl, C₂-C₆ cyanoalkyl, C₃-C₈alkoxycarbonylalkyl, C₃-C₆ cycloalkyl, C₃-C₆ halocycloalkyl, andoptionally substituted phenyl and benzyl wherein the substituents are 1to 3 substituents independently selected from W; R¹⁸ is selected fromthe group H and C₁-C₄ alkyl; or R¹⁷ and R¹⁸, when attached to the sameatom, can be taken together as —(CH₂)₄—, —(CH₂)₅—, or —CH₂CH₂OCH₂CH₂—;R¹⁹ is selected from the group H, C₁-C₄ alkyl, C₂-C₄ alkenyl, C₂-C₄alkynyl, C₂-C₄ alkylcarbonyl, C₂-C₄ alkoxycarbonyl and C₁-C₄alkylsulfonyl; R²⁰ is C₁-C₃ alkyl; R²¹ is selected from the group H,C₁-C₄ alkyl, C₂-C₄ alkenyl and C₂-C₄ alkynyl; R²² is selected from thegroup H, C₂-C₇ alkylcarbonyl, C₂-C₇ alkoxycarbonyl, optionallysubstituted C₁-C₄ alkyl, optionally substituted C₂-C₄ alkenyl, andoptionally substituted C₂-C₄ alkynyl, the substituents selected fromC₁-C₂ alkoxy, —CN, —C(O)R³⁰ and —C(O)₂R²⁷; R²³ is selected from thegroup H, C₁-C₃ alkyl, phenyl, phenyl substituted with W, benzyl andbenzyl substituted with W; R²⁴ is selected from the group H, C₁-C₄alkyl, C₂-C₄ alkenyl and C₂-C₄ alkynyl; R²⁵ and R²⁶ are independentlyselected from the group H and C₁-C₂ alkyl; R²⁷ is selected from thegroup C₁-C₃ alkyl, phenyl and phenyl substituted with W; R²⁸ is C₁-C₃alkyl; R²⁹ is C₁-C₃ alkyl; R³⁰ is selected from the group H, C₁-C₃alkyl, phenyl and phenyl substituted by W; R³² is selected from thegroup C₁-C₃ alkyl; R³⁴ is selected from the group H, Cl, C₁-C₄ alkyl,C₁-C₄ alkoxy, C₁-C₂ thioalkyl and —CN; R³⁵ is selected from the group H,C₁-C₄ alkyl, C₂-C₃ alkylcarbonyl and C₂-C₃ alkoxycarbonyl; R³⁶ isselected from the group phenyl and phenyl substituted with W; W isselected from the group halogen, —CN, —NO₂, C₁-C₂ alkyl, C₁-C₂haloalkyl, C₁-C₂ alkoxy, C₁-C₂ haloalkoxy, C₁-C₂ alkylthio, C₁-C₂haloalkylthio, C₁-C₂ alkylsulfonyl and C₁-C₂ haloalkylsulfonyl; m is 1to 3; n is 1 to 3; p is 1 to 3; r is 0, 1 or 2; t is 2 or 3; u is 1 or2; R_(1′) is —S(O)_(m′)R⁵; R_(2′) is selected from a hydrogen atom, ahalogen atom, —NR^(6′)R^(7′), —S(O)_(n′)R^(8′), —C(O)R⁸, —C(O)OR^(9′),alkyl, haloalkyl, —OR^(9′), or —N═C(R^(10′))(R^(11′)); R^(3′) isselected from a halogen atom or the hydrogen atom; R^(4′) is selectedfrom a halogen atom, haloalkyl, haloalkoxy, —S(O)_(p′)CF₃, or —SF₅;R^(5′) is alkyl or haloalkyl; R^(6′) and R^(7′) are independentlyselected from a hydrogen atom, alkyl, haloalkyl, —C(O) R^(8′),—C(O)OR^(8′), —S(O)_(q′)CF₃; the alkyl portions of which are optionallysubstituted by one or more R^(12′); or R^(6′) and R^(7′) are joined soas together form a divalent radical having 4 to 6 atoms in the chain,this divalent radical being alkylene, alkyleneoxyalkylene oralkyleneaminoalkylene, preferably to form a morpholine, pyrrolidine,piperidine or piperazine ring; R^(8′) is alkyl or haloalkyl; R^(9′) isselected from alkyl, haloalkyl or the hydrogen atom; R^(10′) is selectedfrom R^(9′) or alkoxy; R^(11′) is alkyl or haloalkyl; or is selectedfrom phenyl or heteroaryl that is optionally substituted by one or moregroups selected from hydroxy, halogen, alkoxy, —S(O)_(r′)R^(8′), cyano,R^(8′) or combinations thereof; R^(12′) is selected from cyano, nitro,alkoxy, haloalkoxy, —S(O)_(s′)-alkyl, —S(O)_(s′)-haloalkyl, —C(O)-alkyl,—C(O)-haloalkyl, —C(O)O-alkyl, —C(O)O-haloalkyl, aminocarbonyl,alkylaminocarbonyl, dialkylaminocarbonyl, hydroxy, aminosulfonyl,alkylaminosulfonyl or dialkylaminosulfonyl; X′ is selected from thenitrogen atom, or the radical C—R^(13′); R^(13′) is a halogen atom;R^(14′) is—C(O)CH₃ or —CN; and m′, n′, p′, q′, r′ and s′ represent,independently of one another, the values zero, one or two;
 2. Thecomposition of claim 1, wherein the compound of Formula 1A is ethiproleand the compound of Formulas 1B-G is indoxacarb.
 3. The composition ofclaim 1, further comprising a carrier.
 4. The composition of claim 1,further comprising an additional insecticide.
 5. The composition ofclaim 1, wherein the ratio by weight of the compound(s) of Formula 1A tothe compound(s) of Formulas 1B-G is between 1/32 and 32/1.
 6. Thecomposition of claim 5, wherein the compound of Formula 1A is ethiproleand the compound of Formulas 1B-G is indoxacarb.
 7. The composition ofclaim 1, wherein the composition is in the form of a conventional cropprotection product formulation selected from the group consisting ofwettable powders, emulsifiable concentrates, aqueous solutions,emulsions, sprayable solutions, oil-or-water-based dispersions,suspoemulsions, dusts, seed treatment products, granules for soilapplication or spreading, water-dispersible granules, ULV formulations,microcapsules and waxes.
 8. The composition as claimed in claim 7,wherein the crop is rice.
 9. A synergistic insecticidal composition forcontrolling insects in rice plants which comprises 10 to 80% by weightof ethiprole and indoxacarb.
 10. The composition of claim 9, wherein thecomposition comprises between 10 and 50% by weight of ethiprole andindoxacarb.
 11. A method of controlling insect pests, which comprisesapplying a synergistically insecticidal effective amount of thecomposition as claimed in claim 9 to the insect pests to the riceplants, areas or substrates infested with them.